1, 4-dihydro-1, 4-methanonaphthalene-5, 8-diamine



United States Patent The present invention is directed to aromatizcd cyclopentadiene adducts of p-benzoquinonediimines and more specifically to l,4-dihydro-1,4-methanonaphthalene-5,S-diamines having the structure NHSOzR In this and succeeding formulas, X is bromo, chloro,

fiuoro, methylthio or cyclohexylthio and R is lower-alkyl,;.

phenyl, chlorophenyl or tolyl. By the expression lower alkyl is meant an alkyl radical containing from 1 to 4 carbon atoms, inclusive. The invention also relates to the methods for the preparation of these adducts.

The products of the" present invention are white crystalline solids soluble in many organic solvents such as ethanol, methanol, isopropanol, benzene, toluene and xylene and substantially insoluble in water. The products have many agricultural applications 'such'as inhibition of nitrification and as plant. growth control agents.

by mixing together a p-benzoquinonediimine compound having the structure IIISOzR l NSOzR and cyclopentadiene in the presence of a tertiary amine. I

The reaction is usually carried out in an inert solvent such as benzene, toluene or Xylene. The cyclopentadiene reactant is employed in an excess on a molar basis with respect to the p-benzoquinonediimine reactant, preferably a threefold molar excess or greater. It is also desirable that the cyclopentadiene be freshly prepared. The amount of tertiary amine catalyst employed may vary from a catalytic amount to an amount equimolar with respect to the p-benzoquinonediirnine compound employed. Appropriate tertiary amines include triethylamine, trimethylamine and pyridine. The reaction takes place at a temperature of from 0 to 140 C. over a period of time ranging from 5 minutes to 2 hours to produce the desired 1,4-dihydro-l,4-methanonaphthalene-5,8-diarnine product. The latter usually precipitates in the reaction mixture although some may remain in solution if excess solvent is employed. Excess solvent may be removed by evaporation to precipitate the desired product which may then be recovered by filtration and purified, if desired, by recrystallizing from suitable solvents such as glacial acetic acid, ethanol, methanol, benzene, ethyl acetate the appropriate p-benzoquinonediimine compound is dissolved in an inert solvent and a threefold or greater molar excess of freshly prepared cyclopentadiene and a catalytic amount of triethylamine added thereto. The mixture is The products of the present invention may be prepared methylamine Pyridine' 3,019,259 Patented Jan. 30, 1962 thereafter allowed to cool to room temperature whereupon the desired 1,4-dihydro-l,4-methanonaphthalene-5,8-c1iamine product precipictates as a crystalline solid. The latter is then recovered by filtration and purified according to conventional procedures.

The products of the present invention having the structure NHS 02R fiuoro ehloro bromo 1 N HS 02R may be prepared by heating a 1,4,4a,8a-tetrahydro-1,4- m'eth'anod,8-naphthoquinonediimine compound having the structure in an inert organic solvent in the presence of a catalytic amount of a tertiary amine. Heating is carried out at a temperature of from about to C. for a period of from about 5 minutes to 2 hours. Suitable tertiary amines for use as catalysts include triethylamine, tri- Appropriate solvents for carryingoutthe reaction include benzene, toluene and Xylene. During the heating, a reaction takes place and the desired. 1,4-dihydro-1,4-methanonaphthalene-5,8-diamine is formed .in the reaction mixture. recovered from the reaction mixture by vaporizing off a sufficient amount of the solvent to precipitate the prod- 5 uct, recovering"said product by filtration and recrystalliz- =ing from suitablesolvents such as glacial acetic acid,

The latter is ethanol, methanol,. benzene, ethyl acetate or mixtures thereof In carrying out the reaction, the tetrahydromethanonaphthoquinonediimine compound is heated in an inert solvent at the reflux temperature in the presence of a tertiary amine catalyst until a change in the color of the reactionmixture is observed. Thereafter, the mixture is allowed to cool to room temperature whereupon the desired l,4-dihydro-1,4-methanonaphthalene-5,S-diamine 6-chl0ro-1,4-dihydr0-N,N'-bis(methylsulfonyl) ,4- methanonaphthalene 5,8-diam.ine

NHSOgCH;

NHSOzCH 5.60 grams (0.055 mole) of triethylamine was added then heated to the refiuxtemperature of the solvent and to a boiling solution of 18.1 grams (0.0500 mole) Theoretical of 6-chloro-N,N'-bis(methylsulfonyD-1,4,4a,8a-tetrahydrol,4-methano-5,8-naphthoquinonediimine in 250 milliliters of benzene. The color of the solution changed immediately on the addition of the amine from pale yellow to amber. The mixture was then allowed to cool to room temperature whereupon a 6-chloro-l,4-dil1ydro-N,N'-bis- (methylsulfonyl) 1,4 methanonaphthalene 5,8-diamine product precipitated as a gray solid. The latter was recovered by filtration and purified by treating hot aqueous acetic solution thereof with activated charcoal, cooling to precipitate a light tan crystalline solid and repeatedly recrystallizing said solid with aqueous methanol to obtain a purified product as white crystals melting at 216.5"- 2175 C. The product had elemental analyses in percent as follows:

Carbon Hydrogen Chlorine Nitrogen Sulfur Theoretical Found EXAMPLE 2 N,N'-bis(n-butylsulfonyl) -6-tltlor0-L4-dihydro- 1 ,4 -m th anonaphthalene-S ,8-diam in e Nnsolonaomcmom for 1 hour during which timethecolor-gradually"turned to amber red. At the end ofthis'perio'drthe benzene solvent was removed by vaporizationunder reduced pressure to obtain as 'residuearedfgur'nrny oil. The latter was dissolved in a small amount of hot aqueous acetic acid, the resulting solution treated'with activated charcoal, filtered to remove the charcoal, and cooled to obtain a light tan colored solid. The latter was recrystallized from aqueous acetic acid to obtain an N,N' -bis('nbutylsulfonyl) 6 chloro 1,4 dihydro l,4 rnethanonaphthalene-5,8-diamine product as a white crystalline solid melting at 138-l39.5 C. The "product had elemental analyses as follows:

a so A 6. 21 Found 6. 0s 6.26

EXAMPLE 3 In a reaction carried out in a: manner similar to that above described, the following compounds are prepared:

6 chloro N,N' bis(ethylsulfonyl) 1,4 dihydro-1,4- methanonaphthalene-S,8-diamine by heating 6-chloro-N, N- bis (ethylsulfonyl 1,4,4a',8a tetrahydro -1,4 methano- 5,S-naphthoquinonediimine in the presence of triethylamine catalyst.

6 chloro 1,4 dihydro N,N-bis (isopropylsulfonyl)- l,4-methanonaphthalene-5,S-diamine by heating 6-chloroi 1,4,4a,8a tetrahydro N,N .bis (isopropylsulfonyl) 1,4-

rnethano-S,8=naphthoquinonediimine in the presence, of a catalytic amount of triethylamine.

4 EXAMPLE 4 6 -ch lore-1 ,4 -dihydro-N ,N "-bis( p-ch lorophenylsulfonyl I ,4-methanonaphthalene-5,8-diamine armor-@411 6 drops of triethylamine were added to a well stirred, boiling solution of 3.95 grams (0.00710 mole) of 6-chloro- N,N-bis(p-chlorophenylsulfonyl)-1,4,4a,8a-tetrahydro-l,4- methane-5,8-naphthoquinonediimine in 80 milliliters of benzene. On the addition of the triethylamine the color of the solution changed 7 immediately from yellow to amber. The reaction mixture was then allowed to cool to room temperature whereupon a light tan colored solid precipitated therein. The solid was purified by treating a boiling glacial acetic acid solution thereof with decolorizing .charcoal and recrystallizing from the decolorized solution to obtain a '6 chloro-l,4 dihydro-N,Nf-bis(p-chlorophenylsulfonyl) 11,4 'methanonaphthalene 5,8 diamirie product as a white solid melting at 242-243C.

with decomposition. The product had elemental analyses in percent as follows:

Carbon Hydro- 'j"q -re.'.'.a..n 49.69 ans Found; a 49.83 3.31

EXAMPLE 5 EXAMPLE 6 6-cyclohexylthi0-N,N'-bis(methylsulfonyl) -1,4-dihydr0- 1,4-methan onaphthatene-5,8-diamine NHS 030 H;

v NBSOZCHS 8.2 milliliters (6.6 grams; 0.10 mole) of freshly distilled cyclopentadiene was added to a solution of 6.79

dihydro-l,4-mcthanonaphthalene-5,8-diamine product as a white crystalline solid melting at 183.5 -184 C. The product has elemental analysis as follows:

Carbon Hydrogen Nitrogen Theoretical 51. 56 5. 92 6. 33

Found 51. 33 5. 65 6. 56

EXAMPLE 7 EXAMPLE 3 N,N-bis(methylsulfonyl) -6-methylthi0-1,4-dihydro- 1,4-methanonaphthalene-5,8-diamine NHSOzCHa ems i NHS 020K:

40 milliliters of cyclopentadien'e were added to a solution of 9.25 grams (0.0300 mole) of N,N'-bis(methylsulfonyl) -methylthio-p-benzoquinonediimine in 800 milliliters of benzene. The color of the solution changed from deep red to yellow over a period of about 3 minutes. 5 milliliters of triethylarm'ne were added to the resulting solution and the mixture boiled at reflux temperature for 20 minutes. During the heating, a crystalline solid formed and precipitated in the reaction mixture. The mixture was concentrated by evaporation of the solvent to a final volume of about 400 milliliters and then cooled to room temperature, whereupon a light tan colored precipitate formed. The latter was purified by decolorizing a solution thereof in boiling glacial acetic acid with activated charcoal and recrystallizing from the decolorized solution to obtain an N,N-bis(methylsulfonyl)-6-methylthio 1,4 dihydro 1,4 methanonaphthalene 5,8 diamine product as a white crystalline solid melting at 243.5 -244 C. with decomposition. The product had elemental analyses as follows:

Carbon Hydro- Nitrogen gen i1 t'l .Q 44.90 4.84 7.43 5082x 15 44. 71 4. 79 7. 76

EXAMPLE 9 r 6 EXAMPLE 10 6-fluoro-N,N'-bis(methylsulfonyl) -1,4-methan0naphthalene-5,8-diamine To a well-stirred, boiling solution of 34.6 grams (0.100 mole) of 6-fluoro-N,Nbis(methylsulfonyl)-l,4,4a,8atetrahydro-l,4-methano5,8-naphthoquinonediimine in 5 00 milliliters of benzene is added 2 milliliters of triethylamine. The color of the solution changes immediately from yellow to amber. The reaction mixture is then allowed to cool to room temperature, whereupon a 6- fluoro N,N' bis(methylsulfonyl) 1,4 methanonaphthalene-5,8-diamine product precipitates as a crystalline material. The latter is purified by treating a glacial acetic acid solution thereof with activated charcoal and recrystallizing from the treated solution. The product has a molecular weightof344. 7

EXAMPLE 11 I In similar preparations, theyfollowing compounds are anonaphthalene-5,8-diamine by adding triethylamine to a hot benzene solution of 6-fluoro-N,N-bis (n-propylsulfonyl) l,4,4a,8a tetrahydro 1,4 methano 5,8 naphthoquinonediimine.

6 fluoro N,N bis(secondaly butylsulfonyl) 1,4- methanonaphthalene-5,S-diamine by adding triethylamine to a hot benzene solution of 6-fluoro-N,N-bis(secondarybutylsulfonyl) 1,4,4a,8a tetrahydro 1,4 methano- 5,8-naphthoquinonediimine.

6 fiuoro N,N' bis(o tolylsulfonyl) 1,4 methanonaphthalene-5,8-diamine by adding triethylamine to a hot benzene solution of 6-fiuoro-N,N--bis(o-tolylsulfonyl)a 1,4,4a,8a tetrahydro 1,4 methano 5,8 naphthoquinonediimine. v

- EXAMPLE 12 6-br0m0-1,4-dihydro-N,N'-bis(methylsulfonyl) -1,4-

methanonaphthalene-5,8-diamine To a well-stirred, boiling solution of 40.7 grams (0.100 mole) of 6-bromo-N,N'-bis(methylsulfonyl-l,4,4a,8atetrahydro-1,4-methano-5,8-naphthoquinonediimine in 500 milliliters of benzene is added 2 milliliters of triethylamine. The color of the solution changes immediately from yellow to amber. The reaction mixture is then allowed to cool to room temperature whereupon a 6 bromo 1,4 dihydro N,N' bis(methylsulfonyl) 1,4- methanonaphthalene-S,S-diamine product precipitates as a crystalline solid. The latter is purified as previously described by treating with activated charcoal and recrystallizing from glacial acetic acid. The product has a molecular weight of 405. a

EXAMPLE 13 In similar preparations, the following compounds are prepared:

6 bromo 1,4 dihydro N,N' bis(ethylsulfonyl)- 1,4-methanonaphthalene-5,S-diamine by adding triethylamine to a hot benzene solution of 6abromo-L4-dihydro- N,N' bis(ethylsulfonyl) l,4,4a,8a tetrahydro 1,4- methane-5,8-naphthoquinonediimine.

6 bromo 1,4 dihydro N,N bis(p chlorophenylsulfonyl)-l,4-methanonaphthalene-5,8-diamine by adding triethylamine to a hot benzene solution of16-bromo-L4- dihydro N,N bis(p chlorophenylsulfonyl) 1,4,4a,

8a-tetrahydro-l,4-methano-5,S-naphthoquinonediimine. The products of this invention having the structure lYIHSOzR methyl s cyclohexyl H2 l NHSO R I are useful for maintaining soil fertility by inhibiting the conversion of, reduced nitrogen in the soil to nitrate and nitrite nitrogen. In a representative operation of its use as nitrification inhibitor, an aqueous ammonium sulfate solution containing parts per million by Weight of 6- cyclohexylthio 1,4 dihydro N,N' bis(methylsulfonyl)-1,4-rnethanonaphthalene-5,8-diamine is dipsersed throughout air-dried sandy loam soil, containing essentially no organic material and having been freed of nitrate and nitrite nitrogen by prior'thorough leaching with water. The resulting treated soil is incubated at 25 C. for one week. At the end of this period, the soil is analyzed colorimetrically for nitrate and nitrite nitrogen and compared with a check soil similarly treated with an aqueous ammonium sulfate solution containing no 6-cyclohexythio 1,4 dihydro -'N',N" bi's(methylsulfo-nyl) 1,4- methano-5,8-diamine. It is found that in the soil treated with the composition? containing 6-cyclohexylthio-1,4-dihydro; N,N bis(methylsul fonyl) 1,4 methane 5,8- diamine there is' substantially complete inhibition of nitrification whereas there is no inhibition of nitrification in the check soil.

The products having the structure are useful as aquatic herbicides for the control of undesirable weeds and plants growing in water: In use, good controls of submersed and floating aquatic weeds are obtained when in separate operations, aquatic weeds are exposed to tankscontaining 400 parts by weight of one o f the compounds represented byabove structure per million parts of aqueous medium.

The p benzoquinonediimine compound reactants of the present invention having the formula Nsotn NSOzR may be prepared by mixing a disulfonamide compound having the structure NHSOzR NHSOgR with a slight molar excess of lead tetraacetate in glacial 8 chloride having structure, RSO CI, to produce the disulfonamide having the structure N HS 0 2R fiuoro chloro bromo l NHS 02R When the p-phenylenediamine employed above is 2-fluorop-phenylenediamine, the latter may be prepared by the reduction of 2-fluoro-4-nitroaniline with stannous chloride-hydrochloric acid.

(2.) iWhen X' is methylthio, cyclohexylthio or chloro, an appropriate ring unsubstituted p-benzoquinonediimine compound having the structure mISOZR is mixed with methanethiol or cyclohexanethiol in the presence of a catlytic amount of tertiary amine or with hydrogen chloride in an inert solvent at a temperature of from about 0 C. to 50 C. for a period of from a few minutes to about 1 hour to obtain the desired disulfonamide compound.

The 1,4,4a,8a-tetrahydro-1,4-rnethano-5,8naphthoquinonediimine reactants of the present invention having the formula chloro IiSOzR may be prepared byrnixing together substantially equi-v molar proportions of a benzoquinonediimine having the formula.

fluoro chloro broluo IIIHSOzR NHSOQR wherein X is selected from the group consisting of bromo, chloro, fluoro, methylthio and cyclohexylthio,

and R is selected from the group consisting of loweralkyl, phenyl, chlorophenyl and tolyl.

2. 6-chloro-1,4-dihydro-N,N-bis(methylsulfonyl)-1,4- methanonaphthalene-S,S-diamine.

3. N,N'-bis'(n-butylsulfonyl) 6-ch1oro-1,4-dihydro-1,4 methanonaphthalene-5,8-diamine.-

X l i NS02R with cyclopentadiene in the presence of a catalytic amount of a tertiary amine and maintaining the reaction mixture at a temperature in the range of from to 140 C. for a period of from 5 minutes to 2 hours, wherein X is selected from the group consisting of fiuoro, chloro, bromo, methylthio and cyclohexylthio and R is selected from the group consisting of lower-alkyl, phenyl, chlorophenyl and tolyl.

10 8. A method for preparing a 1,4-dihydro-1,4-methanonaphthalene-5,8-diamine of the formula NHSOzR CH; \l l lHsOzR which comprises heating a 1,4,4a,8a-tetrahydro-1,4- methano-S,8-naphthoquinonediimine compound of the formula at a temperature of from to C.. for a period of from about 5 minutes to 2 hours in the presence of a tertiary amine catalyst, wherein in the above formulas R is selected from the group consisting of lower-alkyl, phenyl, chlorophenyl and tolyl, and wherein Y is selected from the group consisting of bromo, chloro and fluoro.

References Cited in the file of this patent Adams et al.: Bull, Soc. Chim., vol. January 8,

(Ser. 5 pages 24, 29, 30, 34 and 55 to 61,, 1958. 

1. A 1,4-DIHYDRO-1,4-METHANONAPHTHALENE-5,8-DIAMINE OF THE FORMULA 